Balancing hydrocarbon conversion



Jan. 25,1944. c. w. NYsEwANDER l 2,339,874 I BALAvN-CING HYDROCARBON CONVERSION Filed Jan. 51, 1941 Patented Jan. 25,

BALANcmG nrnaocaaoN coNvEnsroN Cecil W. Nysewander, Highland, Ind., assigner to Standard Oil Company,

ration of Indiana Appuoauon January 31, 1941, sonal No. 376,792

z claims. (ci. 19e-52) ular mass of varying particle size, I. have a screen size of l mesh to 300 or 4 00meslfi f This invention relates to the catalytic conversion of hydrocarbon oils and particularly the conversion of gas oils into highknock rating gasoline by the action of solid, heterogeneous catalysts on the gas oil vapors at elevated con#` version temperature. The invention also relates to a combination of catalytic and non-catalytic thermal conversion operations to produce gasolines of certain desired specifications. Y

One object of the invention is to provide a ilexible process for converting heavy oils into gasoline with different distillation and antiknock characteristics whenever desired. Another object of the invention is to provide a process and apparatus for producing in addition to gasoline certain of the lighter hydrocarbons desirable in gasoline for winter use, particularly the butanes and pentanes. The terms butanes and pentanes used herein will be understood to include the unsaturated hydrocarbons corresponding thereto, i. e., the butylenes and pentylenes. respectively.

'I'he invention is illustrated by a drawing which forms a part oi' this specification and which shows diagrammatically the layout for a plant designed to carry out the process.

Referring to the drawing: the charging stock which may be Mid-Continent gas oil, for example of 32.2 A. P. I.. is introduced at I0 and forced by pump il to one or more of the pipe heating furnaces I2, il and I4. Two -principal methods of operation areemployed which will be desig-w nated as series flow and parallel dow. The series now operation is employed where a high yield of gasoline is desired having average volatility. Parallel flow operation is employed where a gasoline of high volatility is required or where it is desired to produce butanes and pentanes in addition to gasoline.

- Series flow Describing the series flow operation rst: the charging stock is passed through furnace i2, valve I being closed.v The oil is vaporized and the vapors are heated to the desired conversion temperature, usually between 850 and 1050 F. For most stocks a temperature in the range of 900 to 950 F. is satisfactory.` Oil vapors leaving the furnace at a temperature within the range of 900 to 95011". are contacted Aat such .temperature in reactor i8 with powdered catalyst introduced by line il and dispersed in the vapor stream. The catalyst is a porous, refractory. solid material, generally of siliceous nature. It may be in any suitable state of subdivision, for example, in the form of a fine powder or a gran- Chicago, Ill., a corpodepending onthev type of apparatusemployed and the mode of contacting.' Usually a-.screen size of 40 to 200 mesh is convenient. f IThe catalystsare inorganic substances,.usally\ oxides, for` example, silica, alumina, magrlsixao` and in general the oxides of the .metals ofGroups II to VI of the Periodic Table. V For `use vin* cracking, mixed oxides are commonly employed', such Y as alumina deposited on active silica, and various combinations of alumina, zirconia, magnesio. and .y y

silica. Co-precipitated alumina on silica or magnesia on silica are suitable and silica gelspref bentonite, .fullers earth,.etc. may also be em ployed. The catalyst is generally dehydrated byA ignition and it is preferable to preheat the cataf lyat before introducing it into the on stream. ,i v

Various means may be employed for feedingthe catalyst at the desired rate, .for example, screw pumps, star feeders and other types. of automatic feeders may be used. The catalyst may be suplplied under pressure from a tower or standpipe;

not shown, in order to overcome the back pres'- sure of the vapors in the transfer lines i8, i9

and 20, and assuresl oonstantVsteady introduc# f I tion of catalyst to the stream of oil vapors.v

Returning now to the drawing, the mixturel I of vapors and catalyst, containing for example about 1 to 10 vpounds of catalyst per pound of vapors, passes through line i8 into reactor I6 where sufilcient time of contact is provided to effect the desired conversion. usually about 20 to 50% of the oil charged. 'I'he catalyst is malntained in the reactor for a longerperlod of time than the vapors due to the phenomena of sedimentation and hindered settling.y This is called the catalyst residence time. It may be varied by varying the velocity of the vapors passing upward through the reactor, the lower the velocity. the longer the catalyst residence time. Catalyst residence times of ya to .10 minutes are suitable with lsuspended catalysts.

Spent catalyst and vapors pass by line 2i to centrifugal separating device 22 where most of the catalyst is separated from the vapors. and falls to the discharge line 23. Vapors substen 'tially free of catalyst pass byline 2i to fractiona tor 25 where gasoline and lighter hydrocarbons are removed through vapor line 28. The gasoline vapors are thence conducted by manifold 2l to stabilizer 28 where the gasoline is separated from the undesired gases particularly propane and lighter gases. The stabilizer Il'is preler.

ably operated 4at an elevated pressure. usually simple'liquid pump. A rebollinacoil atthdbote.

tomo! stabilizer!! anda coll at-theltbp.

vide thc` necessary heat and coolnot SvhOwna pro. uw e. I" 9m to so F.

ins for fractionation. from the stabilizers: une and drawn by line Il. The.

. Unconvertcdflfheavy.

. ywhich may not have heated again to a hiah `conversion tain butanewhichia `ot that the essonne. mi later. r.

drawn 'from :l andere passeatnrough-vax ne valves ju u beine-:closedf 011 contlnlnl 'in QWMGHL" BD,

for example about 950 I., conducted by transfer line IIA-to M. ditimllliwyli il blm'oll ratio 'ci campeona u; Aoil merced faboutthe salnefnagthatinreactoril. Ifdesired. l bovenaan be addedzatjj and the catalyst a monactiveltype.'

Y ployed in calculating the space velocity. Wherethe catalyst is in the form of a powder them- 7o' of conditions fmay' be obtainedibyactivity oi' the catalyst as indicated. by

the amount o!l the catalyst-1.ve.. the catalyst to l `oil ratimbyvincreaslnlr';theY temperature or by reducing` the space velocity;` 'velocitywenn 1 1 apparent volume of the catalyst is usually-ern@l responding volume oi the catalystmay'be determined from its weight and density. In general d a space velocity of about l is satisfactory. Space velocities oi' 0.1 to 3cr even as high may be used. however.

v operation just described. Afvirginaz" A. nr.

site: the desiree reaction has taken in toheater wherev-.thevfapors are alain heated' .'lhepreasure-isfalsosuitably increased at this point'by pump vI l. "The pressure in the catltic it. )Fand 41. is generallyouiteglow of ,withdrawn by tar une :awhile o@ fraction boiling above the range out through pump!" and back to heater In thi! manner the heavy vaporizable fractionstarsre- Mid-Continentzgas' 'cilwas charted-by line, il;

molino; v'fpdunds., inthe. .second pcsstne yield nl -to37% .andinthe third throulh -l1:-'.yieid was increased to 46.7%. cracking 4of the residue -from reactor carried outat; '150V pounds per square inch 'e charging stock 'gadditi nal butane was produced above tha gasoline 'I'he knock rating or Aga'lat'ilixieproduced was '12.2 C. l". R.'i dry gas produced was 9.8%' s f by* da; ;`-o1 harsins In addition.

l 13.556 tar 'suitable-"for iuelfoll was produced and divided substantially in proportion to the reactor volume and charged into furnaces I2. I l and il in parallel. It is passed with catalysts through reactorsyil, 3l and 41 substantially as in the A series operation .except that in this case identical conditions will usually'be-cmplyed in each reactor'with respect to temperature and catalyst to oil ratio. .The heaw-stock separated at thek bottom of tractionatorsvzl, Il and 5I is con- `lducted by lines Il. Il and-to manifold Il leading to pump. by. which it is charged to .:iifpounds-persquare'ich or j per. square inch, and the u vinch.'.p'refei'al'lly .about honneur u une,

cycled tocompletion, the only producta--elimi 'y nated being` the tar at It and-.gasoline andilas..

'I'he following .data ,will illustrate the'z leriea y d Pf vIt yielded an additional 36.2% of Total yield, vol. per cento! charge the Lreactors 'where ythe cracked in 'soaking 'drum llfunder'V conditionslv`r sans# slmilarto those previously describedexcept that somewhat lower temperatures may' be `employed if desired. The heavy recyclesiock is returned to the furnace byline and pump It as before until theoll is completely; converted into gasoline. e

gas and tar...

As an exemple ofv thisl type of eperetien the following data were obtained; charging the same sist usueuy or e verticallyv ernennen drum inte e which the catalyst is introduced at th'ebottom withair lor other oxidizinggas, for example a mixture ofair and iiuegas 'and the carbonacecus matter is burned .from the catalyst particles while they pass'upwardly through the drum, care beingv taken tocontrol the temperatureV to'prevent'its f rising 'above the vpoint at which: the" Catalyst will stock by line I0 at the same temperature, i.`e.-,v

900 F.. there was produced by catalyticcracking in reactors, Il and "146.3% ofgasoIine'.A A i space velocity of 0.73 was employed to obtain this conversion. 'I'hermal cracking of the heavy products'infurnace il anddrum Il produced anuadditional 31.1% of gasoline, making a total yieldfof '17.4% of gasoline on the gas oil charged to the'prooess. In addition, there was produced f A7.5% of butane. 13.6% of tar. and 9.7%iof dry gas. The knockflating of the gasoline was 73.9 compared with 12;2produced by the series lThe significant difference between the two methods, series and parallel, lies in the product zdistriimtlon` of the gasoline which may be indi- "f conveniently by the distillation range Tibo!!! following table:

lfarallel per cent. ine

Reid vapor pressure of the above gasol myauesesedr j type of Pilertio Y vapors pass v "through, 1191811? ihz a downward direction. n.,.mevmg .bed

.v discharged `faiatli'e bottom of the bed. The

" l' data in the examples Just given were obtained by such a moving bed type of operation. When employing a stationary bed it is desirable to regenerate the catalyst at intervals by diverting the flow of hydrocarbon vapors to a fresh catalyst l drum and blowing air through the spent catalyst ,l

to restore its activity at intervals, usually of usuauyseusfaetory end-certain catalysts maybe regenerated -atsomewhat higher temperatures.

e. g., 1400 to1600 F. The regenerated catalyst'. l j preferably while still hot from the regenerator,

is returned to the inlet of the reactors anddis-- persed inthehydrocarbon oil vapors as 'previously l,

described: 4

In theser'ies operation, itma'ybe desirable to up catalyst for the earlier stages of the system may be obtained by advancing the catalyst successively from' the later stages of the system. In general, however, I prefer to combine all spent catalyst from 23, Il and BI and regenerate it in a single apparatus, thereafter distributing the re-` generated catalyst to the separate stages of the system.

It will y bef. `observed from the foregoing data that my processjand apparatus provide a means for making a'gasoline of `low volatility or high volatility as desired-from the same charging stock and underw substantially the same conditions by simply altering the flow of the oil through the process. In addition to making high volatility gasoline the parallel ilow operation also produces an excess of butane which is sometimes desired for blending with other gasoline stocks of insumcient volatility. The excess butane may also be stored separately and employed in blending winter gasolines. The adaptability ofmy process enablea'the reilner to changequickly from the manufacture of low volatility summer gasolines high volatility winter gasollnes when desired fandfvice'versa. v By the use of my process the rehnerfgis'gnot., required to vcarry over large stocks of high volatility'gasoline fromy the summer season -to the winter' season-because the desired volatility can be madefcurren'tly by simply shifting the process from seriesfoperation ton parallel operaoperatlon may-also be fresh catalyst being continually or intermittehtly charged air-tiratori minutes to 2 hours duration. Where moving l bed or granular catalyst is employed, the catalyst is continuously or intermittently introduced into the top of the reaction chamber and flows downwardly to the outlet where it is withdrawn and regenerated in a separate apparatus by blowing with air, the regenerated catalyst being returned to the reactor inlet.'

In suspended catalyst operation illustrated in tin;

though I have described my invention' with respect tocertain applications'thereof. it should be understood that it is intended to be limited only -by the following claims. Thus I may ernploy various modifications such as lconducting the catalytic cracking operations inthe preseneeof hydrogen and/orrecycle gases added to the chargingstock. Other -modiflcationswill be apparent to those skilled in the art. y

I claim:

l. The process of catalytically converting heavy hydrocarbon oils into gasoline in a. system employing a plurality of catalytic reaction stages which comprises operating saidstages in series for a selected period of time by contacting the vapors of said oils at conversion temperature with a refractory, solid ilnely divided, suspended cracking catalyst, thereby effecting a partial con- Y version of the heavy oilsinto gasoline. separat- 1ing hydrocarbon vapors from catalyst, fractionating said vapors to separate gasoline from unconverted oil, contacting the unconverted voil with additional powdered catalyst ina second reaction 4f! l stage at conversion temperatures, separating the gasoline produced in said second reaction stage from catalyst and unconverted heavy oils, conond stage with 'additional conversion catalyst suspension in athird reaction stage, separating the gasoline from catalyst and heavier products of said third reaction stage, subjecting thevheavy products from said `third reaction stage to thermal conversion with recycling to completion, and

blendinggasoline from said thermal conversionA with gasoline produced in said catalytic conversion operations, to produce said gasoline of relatively low volatility, and periodically operating said catalytic conversion stages in parallel to produce gasolineo!` relatively high volatility bydi- 2',sa9,a74 y rectly charging each ofjsaid catalyticistages with,V ,y

said heavy hydrocarbon oil, separati'ngcatalyst tacting said heavy oils thus produced in said secy and thermal conversion operations to produce theand fractionating theproducts after each stage, charging the fractions heavier than gasoline from each vstage to said thermal conversion step and blending gasoline fractions from the catalytic cEcn. w. NYSEWANDER. 

